Utilizing optical spectroscopy and 2',7'-difluorofluorescein to characterize the early stages of cement hydration

The increasingly sophisticated nature of modern, more environmentally friendly cementitious binders requires a better understanding and control particularly of the complex, dynamic processes involved in the early phase of cement hydration. In-situ monitoring of properties of a constantly changing system over a defined period of time calls for simple, sensitive, fast, and preferably also non-invasive methods like optical spectroscopy. Here, we exploit the time-dependent changes in the absorbance and fluorescence features of the negatively charged optical probe 2',7'-difluorofluorescein (DFFL) for the study of the hydration processes in pastes of white cement (WC), cubic tricalcium aluminate (C₃A), and tricalcium silicate (C₃S), the main phases of cement, and in pastes of quartz (Q) over 24 h after addition of the dye solution. For comparison, also conventional techniques like isothermal heat flow calorimetry were applied. Based upon the time-dependent changes in the spectroscopic properties of DFFL, that seem to originate mainly from dye aggregation and dye-surface interactions and considerably vary between the different pastes, molecular pictures of the hydration processes in the cement pastes are derived. Our results clearly demonstrate the potential of optical spectroscopy, i.e., diffuse reflectance, steady state and time-resolved fluorometry in conjunction with suitable optical reporters, to probe specific hydration processes and to contribute to a better understanding of the early hydration processes of cement at the molecular scale.